Adhesive composition for use in roofing materials

ABSTRACT

A moisture curable, non-bitumen based and non-asphaltic based adhesive includes an extender, a compatibilizer, and a polymer, wherein the polymer includes reactive silyl groups.

The present disclosure is a continuation of U.S. patent application Ser.No. 16/573,050 filed Sep. 17, 2019, which in turn claims priority onU.S. Provisional Patent Application Ser. No. 62/733,880 filed Sep. 20,2018, which are incorporated herein by reference.

The disclosure relates in general to an adhesive composition, and moreparticularly to an adhesive composition for use in roofing materials.

BACKGROUND ON THE INVENTION

Flexible roofing membranes are commonly formed of bitumen that has beenmodified by thermoplastic polymers such as block elastomers, such asstyrene butadiene styrene (SBS), styrene ethylene butadiene styrene(SEBS), etc., or plastomers, such as polyolefin, for example, PPA, EVA,PPI, Amorphous polyolefin (APAO), etc.

In view of the prior art, there remains a need for an improved moisturecurable non-bitumen based adhesive that can be used in roofingmaterials.

SUMMARY OF THE DISCLOSURE

The disclosure is directed to a moisture curable, non-bitumen andnon-asphaltic based adhesive. The moisture curable, non-bitumen andnon-asphaltic based adhesive includes extender, compatibilizer andpolymer. The polymer includes reactive silyl groups. In one non-limitingembodiment, the moisture curable, non-bitumen and non-asphaltic basedadhesive is a one part adhesive. In another non-limiting embodiment, themoisture curable, non-bitumen and non-asphaltic based adhesive issubstantially free of volatile organic compounds (i.e., less than 0.5wt. %, typically less than 0.1 wt. %, and more typically less than 0.05wt. %), and/or is substantially free of isocyanate groups (i.e., lessthan 0.5 wt. %, typically less than 0.1 wt. %, and more typically lessthan 0.05 wt. %). In one non-limiting example, the moisture curable,non-bitumen and non-asphaltic based adhesive is substantially free or is100% free of asphalt, bitumen, coal tar, and volatile solvents. Inanother non-limiting example, the moisture curable, non-bitumen andnon-asphaltic based adhesive is substantially free or is 100% free ofasphalt, bitumen, coal tar, volatile solvents, and isocyanate groups.

In another and/or alternative non-limiting aspect of the disclosure, oneor more of the reactive silyl groups in the polymer are selected fromthe group consisting of a polyether having reactive silyl groups, apolyurethane having reactive silyl groups, and a polyester havingreactive silyl groups. Non-limiting examples of polymer includingreactive silyl groups include silylated polyurethane, silylatedpolyethers, silylated acrylics, and silylated polyesters. In onenon-limiting embodiment, the silylated polymers or silyl-terminatedpolymers can include two or more reactive silyl groups. In onenon-limiting specific example, the polymer includes alpha,omega-telechelic silane-terminated polymers. In another non-limitingembodiment, the polymer content in the moisture curable, non-bitumen andnon-asphaltic based adhesive is generally at least about 10 wt. %, andtypically 10-31 wt. % (and all values and arranges therebetween). In onenon-limiting example, the polymer content in the moisture curable,non-bitumen and non-asphaltic based adhesive is 10-25 wt. %, andtypically 12-20 wt. %.

In another and/or alternative non-limiting aspect of the disclosure,non-limiting examples of moisture cure isocyanate terminated polymersthat can be used to form polymer having reactive silyl groups includeany moisture curable polyurethane or polyurea prepolymer comprised ofexcess isocyanate reacted with one or more active hydrogen containingmolecules.

In another and/or alternative non-limiting aspect of the disclosure,non-limiting examples of active hydrogen-containing molecules useful inthe preparation of polyurethane prepolymers include, but are not limitedto, one or more of polyether, polyester, polyalkyldiene polyols, and/orderived from reaction of excess of such polyols, alone or in combinationwith isocyanate functional compounds. The polyols can be diols and/ortriols. Non-limiting examples of polyols that can be used includepolyoxypropylene polyol, polyalkylene polyol, and polypropylene glycols.For example, polyether diols having high equivalent weights are used.One non-limiting polyol that can be used is polyether diols. One suchnon-limiting specific example is polyether diols with equivalent weightsranging from greater than about 200 to about 20000 (and all values andranges therebetween), and typically about 500 to about 5000 can be used.

In another and/or alternative non-limiting aspect of the disclosure,non-limiting examples of active hydrogen-containing molecules useful inthe preparation of polyurea prepolymers include, but are not limited to,one or more of primary or secondary amine functional polyether,polyester, or polyalkyldiene polymers, and/or derived from reaction ofexcess of such primary amine functional polymers, alone or incombination with isocyanate functional compounds. The amine functionalpolymers can include difunctional or trifunctional. Non-limitingexamples of useful amine functional polymers includepolyoxypropyleneamine, polyalkyleneamine, and/or amine terminatedpolypropylene glycols. For example, polyether diamines having highequivalent weights can use used. One such non-limiting specific exampleis polyether diamines with equivalent weights ranging from greater thanabout 200 to about 20000 (and all values and ranges therebetween), andtypically 500-5000 can be used.

In another and/or alternative non-limiting aspect of the disclosure, theextender can be used to facilitate affinity with both the moisturecurable, non-bitumen and non-asphaltic based adhesive and a roofingmembrane. The extender is believed to be an important mechanism forproviding adhesion to the roofing membrane. The extender can optionallyprovide viscosity reduction and/or increased permeability that issuitable for improved workability and/or adequate cure throughout themoisture curable, non-bitumen and non-asphaltic based adhesive.Non-limiting extenders suitable for use in the moisture curable,non-bitumen and non-asphaltic based adhesive include esters of polybasicacids and polyhydric alcohol, or fatty acid oils/esters, oraromatic/aliphatic carboxylic acid esters, among others. Specificnon-limiting extenders include, but are not limited to, triethyleneglycol di-(2-ethylbutyrate), triethylene glycol di-(2-ethylhexanoate),triethylene glycol diheptanoate, tetraethylene glycol diheptanoate,dihexyl adipate, dioctyl adipate, hexyl cyclohexyladipate, mixtures ofheptyl and nonyl adipates, diisononyl adipate, heptyl nonyl adipate,dibutyl sebacate, isononyl benzoate, nonyl benzoate, isodecyl benzoate,decyl benzoate, 2-propylheptyl benzoate, isoundecylbenzoate, isotridecylbenzoate, di-heptyl cyclohexanoate, di-2-ethylhexyl cyclohexanoate,di-n-nonyl cyclohexanoate, diisononyl cyclohexanoate, di-n-decylcyclohexanoate, diisodecyl cyclohexanoate, di-2-propyl heptylcyclohexanoate, diheptyl adipate, dioctyl adipate, diisononyl adipate,diisodecyl adipate, di 2-propylheptyl adipate, dipropylene glycoldibenzoate, diethylene glycol dibenzoate, triethylene glycol dibenzoate,or mixtures thereof. Generally, the extender content in the moisturecurable, non-bitumen and non-asphaltic based adhesive is at least 4 wt.% and up to about 45 wt. % (and all values and ranges therebetween). Inone non-limiting embodiment, the extender content in the moisturecurable, non-bitumen and non-asphaltic based adhesive is 5-40 wt. %,typically 8-30 wt. %, more typically 10-25 wt. %, and even moretypically 12-18 wt. %.

In another and/or alternative non-limiting aspect of the disclosure, thecompatibilizers can be used to compatibilize dissimilar materials toresult in stable mixtures and good adhesion and stability properties ofthe membrane. The compatibilizers can be used to address the limitedcompatibility of adhesive polymers and extenders with bitumen/asphalticroofing products, which limited compatibility can lead to unstableand/or too aggressive membrane penetration, thereby resulting invariable and/or inferior long term adhesion properties. In onenon-limiting embodiment, compatibilizers of moderately polar componentscan be used. Non-limiting examples of compatibilizers include, but arenot limited to, polyols such as, but not limited to, adipate andcarbonate glycols, and/or olefinic glycols. Non-limiting specificexamples of compatibilizers include polyoxyalkylene polyols (also calledpolyether polyols or oligoetherols, which are polymerization products ofethylene oxide, 1,2-propylene oxide, 1,2- or 2,3-butylene oxide,oxetane, tetrahydrofuran or mixtures thereof, possibly polymerized withthe aid of a starter molecule having two or more active hydrogen atoms,for example water, ammonia or compounds having a plurality ofoxygen-hydrogen (OH) or nitrogen-hydrogen (NH) groups). Specificnon-limiting examples are polycarbonate polyol, carbonate glycolsparaffinic and olefinic glycols, and/or adipate glycol (e.g., diethyleneglycol adipate, ethylene glycol adipate, propylene glycol basedpolyether polyol diol, etc.). In one non-limiting embodiment, thecompatibilizer in the moisture curable, non-bitumen and non-asphalticbased adhesive is at least 2 wt. % and up to 45 wt. % (and all valuesand ranges therebetween). In one non-limiting embodiment, thecompatibilizer content in the moisture curable, non-bitumen andnon-asphaltic based adhesive is 2.1-42 wt. %, typically 3-40 wt. %, moretypically 4-32 wt. %, still more typically 5-24 wt. %, and even moretypically 8-15 wt. %. The weight ratio of the extender to thecompatibilizer in the moisture curable, non-bitumen and non-asphalticbased adhesive is 1:1 to 5:1 (and all values and ranges therebetween),and typically 1:1-3:1, and more typically 1.1:1-2:1. In one non-limitingformulation, the extender constitutes a larger weight percent than thecompatibilizer in the moisture curable, non-bitumen and non-asphalticbased adhesive.

In another and/or alternative non-limiting aspect of the disclosure, themoisture curable, non-bitumen and non-asphaltic based adhesive includesone or more of adhesion promoter, antioxidant, catalyst, dehydrationagent, filler and/or tackifier.

In another and/or alternative non-limiting aspect of the disclosure, theadhesion promoter, when included in the moisture curable, non-bitumenand non-asphaltic based adhesive, is used to improve the adhesion of themoisture curable, non-bitumen and non-asphaltic based adhesive with aroofing membrane (e.g., modified bitumen membrane, EPDM membrane, etc.).Non-limiting adhesion promoters include silane adhesion promoters (e.g.,N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, etc.). The one or moreadhesion promoters, when used, are provided to facilitate adhesion ofthe moisture curable, non-bitumen and non-asphaltic based adhesive to avariety of substrates. Non-limiting examples of adhesion promoters thatcan be used in the moisture curable, non-bitumen and non-asphaltic basedadhesive include, but are not limited to, silane coupling agents havinga functional group such as a mercapto group, an epoxy group, a carboxylgroup, a vinyl group, an isocyanate group, isocyanurate, halogen, or anamino group. Specific non-limiting examples of adhesion promotersinclude isocyanate group-containing silanes such as3-Isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane,3-isocyanatopropylmethyldiethoxysilane, and3-isocyanatepropylmethyldimethoxysilane; amino group-containing silanessuch as (3-aminopropyl)trimethoxysilane, (3-aminopropyl)triethoxysilane, (3-aminopropyl)triisopropoxysilane,(3-aminopropyl)methyldimethoxysilane,(3-aminopropyl)methyldiethoxysilane,N-(2-aminoethyl)-3-aminopropyltrimethoxysilane,N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane,N-(2-aminoethyl)-3-aminopropyltriethoxysilane,N-(2-aminoethyl)-3-aminopropylmethyldiethoxysilane,N-(2-aminoethyl)-3-aminopropyltriisopropoxysilane,(3-ureidopropyl)trimethoxysilane,N-phenyl-3-aminopropyltrimethoxysilane,N-benzyl-3-aminopropyltrimethoxysilane, andN-vinylbenzyl-3-aminopropyltri ethoxysilane; mercapto group-containingsilanes such as (3-mercaptopropyl)trimethoxysilane,(3-mercaptopropyl)triethoxysilane,(3-mercaptopropyl)methyldimethoxysilane, and(3-mercaptopropyl)methyldiethoxysilane; epoxy group-containing silanessuch as (3-glycidoxypropyl)trimethoxysilane,(3-glycidoxypropyl)triethoxysilane,(3-glycidoxypropyl)methyldimethoxysilane,2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and2-(3,4-epoxycyclohexyl)ethyltriethoxysilane; vinyl type unsaturatedgroup-containing silanes such as vinyltrimethoxysilane,vinyltriethoxysilane, (3-acroyloxypropyl)methyltriethoxysilane;halogen-containing silanes such as (3-chloropropyl)trimethoxysilane;isocyanurate silanes such as tris(trimethoxysilyl)isocyanurate,polysulfanes such as bis(3-triethoxysilylpropyl)tetrasulfane, and thelike can be also used as the adhesion promoter. In one non-limitingembodiment, the adhesion promoter content in the moisture curable,non-bitumen and non-asphaltic based adhesive is at least 0.01 wt. % andup to 4 wt. % (and all values and ranges therebetween), typically 0.01-2wt. %, more typically 0.01-1.5 wt. %, even more typically 0.01-0.5 wt.%, and still even more typically 0.01-0.1 wt. %.

In another and/or alternative non-limiting aspect of the disclosure, theantioxidant, when included in the moisture curable, non-bitumen andnon-asphaltic based adhesive, is used to improve the stability of themoisture curable, non-bitumen and non-asphaltic based adhesive.Non-limiting antioxidants that can be used include Irgonox® 1010 (BASF)(pentaerythritoltetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), Irgonox® 245(BASF) (ethylene bis (oxyethylene)bis-(3-(5-tert-butyl-4-hydroxy-m-tolyl)-propionate), and CYASORB®(Cytec) Ultraviolet (UV) stabilizers (e.g., amine light stabilizerconcentrate in polypropylene, 2-Hydroxy-4-n-octoxybenzophenone,1,6-Hexanediamine, N,N′-bis(2,2,6,6-tetramethyl-4-piperidinyl)-,Polymers with morpholine-2,4,6-trichloro1,3,5-triazine, etc.). In onenon-limiting embodiment, the antioxidant content in the moisturecurable, non-bitumen and non-asphaltic based adhesive is at least 0.001wt. % and up to 5 wt. % (and all values and ranges therebetween),typically 0.01-5 wt. %, more typically 0.01-1 wt. %, and even moretypically 0.01-0.6 wt. %.

In another and/or alternative non-limiting aspect of the disclosure, thecatalyst, when included in the moisture curable, non-bitumen andnon-asphaltic based adhesive, is used to promoting curing of thesilyl-terminated polymer. Non-limiting catalysts that can be usedinclude dibutyltin dilaurate, dibutyltin oxide, dimethylcyclohexylamine(DMCHA), dimethylethanolamine (DMEA), dioctyltin mercaptide, and N-tinmercaptides. In one non-limiting embodiment, the catalyst content in themoisture curable, non-bitumen and non-asphaltic based adhesive is atleast 0.01 wt. % and up to 1 wt. % (and all values and rangestherebetween), typically 0.01-0.5 wt. %, and more typically 0.1-0.4 wt.%.

In another and/or alternative non-limiting aspect of the disclosure, thedehydration agent, when included in the moisture curable, non-bitumenand non-asphaltic based adhesive, is used to improve storage stabilityof the moisture curable, non-bitumen and non-asphaltic based adhesive.Dehydrating and drying methods include 1) heat drying in the case thatthe components are solids such as powder and 2) vacuum dehydration anddehydration using a substance such as synthetic zeolite, active alumina,silica gel, quick lime, and magnesium oxide in the case that thecomponents are liquids. The moisture curable, non-bitumen andnon-asphaltic based adhesive can be stabilized by adding a lower alcoholsuch as methanol and ethanol; or an alkoxysilane compound such asn-propyltrimethoxysilane, vinyltrimethoxysilane,vinylmethyldimethoxysilane, methyl silicate, ethyl silicate,(3-mercaptopropyl)methyldimethoxysilane,(3-mercaptopropyl)methyldiethoxysilane, and(3-glycidoxypropyl)trimethoxysilane, an organosilane possessing areactive vinyl group and/or a silyl group (e.g., trimethoxyvinylsilane,vinyltrimethoxysilane, etc.). In one non-limiting embodiment, thedehydration agent content in the moisture curable, non-bitumen andnon-asphaltic based adhesive is at least 0.05 wt. % and up to 2 wt. %(and all values and ranges therebetween), typically 0.05-1.5 wt. %, andmore typically 0.05-0.4 wt. %.

In another and/or alternative non-limiting aspect of the disclosure, thefiller, when included in the moisture curable, non-bitumen andnon-asphaltic based adhesive, is used as needed in the range not toimpair the properties of the moisture curable, non-bitumen andnon-asphaltic based adhesive. Fillers may be used as a reinforcement, UVstability, flame retardancy, color, etc. Non-limiting examples offillers include wood meal, walnut shell flour, rice hull flour, pulp,cotton chips, mica, graphite, diatomaceous earth, china clay, kaolin,clay, talc, fumed silica, precipitated silica, silicic anhydride, quartzpowder, glass beads, calcium carbonate, magnesium carbonate, titaniumoxide, carbon black, glass balloons, aluminum powder, zinc powder,asbestos, glass fiber and/or carbon fiber. In one non-limitingembodiment, the filler content in the moisture curable, non-bitumen andnon-asphaltic based adhesive is at least 20 wt. % and up to 70 wt. %(and all values and ranges therebetween), typically 20-60 wt. %, andmore typically 20-40 wt. %.

In another and/or alternative non-limiting aspect of the disclosure, thetackifier, when included in the moisture curable, non-bitumen andnon-asphaltic based adhesive, is used to increase formulation tack so asto add adhesive strength to a substrate. Non-limiting tackifiers thatcan be used includes virtually any hydrocarbon oil or mixture thereofthat is commonly used in bitumen and/or coal tar compounding or as aplasticizer and processing aid, such as, but not limited to, anaphthenic oil or aromatic resins containing varying aromatic contents,such as aromatic resins, can be used but is not necessary. The tackifiershould be compatible with other components of the moisture curable,non-bitumen and non-asphaltic based adhesive. Specific non-limitingexamples of tackifiers include aromatic resins such as C9, C5, and/orcoumarone indene resins, naphthenic oils such as Sundex 790T fromSunoco, ProGuard Altranap 1000 from Lynden Oil Co., and Amplex® 100 fromCitgo. In one non-limiting embodiment, the tackifier content in themoisture curable, non-bitumen and non-asphaltic based adhesive is atleast 0.01 wt. % and up to 30 wt. % (and all values and rangestherebetween), typically 0.5-5 wt. %, and more typically about 1-3 wt.%.

In another and/or alternative non-limiting aspect of the disclosure, themoisture curable, non-bitumen and non-asphaltic based adhesive canoptionally include one or more other additives such as, but not limitedto, stabilizer, ultraviolet absorber, metal deactivator, lightstabilizer, thixotropic agent, amine type radical chain inhibitor,phosphorus-containing peroxide decomposer, lubricant, pigment, foamingagent, anti-foaming agent, flame retardant and/or antistatic agent. Thetotal content of these optional additives in the moisture curable,non-bitumen and non-asphaltic based adhesive generally does not exceed 5wt. %, and typically does not exceed 2 wt. %

In another and/or alternative non-limiting aspect of the disclosure, themoisture curable, non-bitumen and non-asphaltic based adhesive isformulated to form a peel strength with a roofing membrane (e.g.,modified bitumen membrane, EPDM polymer membrane, etc.) that is greaterthan 1 pound per linear inch (pli), and typically greater than 2 pli. Inone non-limiting embodiment, the moisture curable, non-bitumen andnon-asphaltic based adhesive is formulated to form a peel strength witha roofing membrane of 1-6 pound-force (lbf) after one week ofapplication (and all values and ranges therebetween) and 1.8-7 lbf afterthree weeks of application (and all values and ranges therebetween),typically 1.5-5.5 lbf after one week of application and 2-5.6 lbf afterthree weeks of application, and more typically 1.6-5 lbf after one weekof application and 2.1-5 lbf after three weeks of application.

In another and/or alternative non-limiting aspect of the disclosure, themoisture curable, non-bitumen and non-asphaltic based adhesive has atensile strength at point of breakage per ASTM D 413 of at least 70 ksiand up to 250 ksi (and all values and ranges therebetween), and anelongation of at least 250% and up to 800% (and all values and rangestherebetween). In one non-limiting embodiment, the moisture curable,non-bitumen and non-asphaltic based adhesive has a tensile strength atpoint of breakage per ASTM D 413 of 72-190 ksi and an elongation of300-750%, and typically 77-150 ksi and an elongation of 340-730%.

In another and/or alternative non-limiting aspect of the disclosure, themoisture curable, non-bitumen and non-asphaltic based adhesive isformulated to a have a substrate failure of less than 10% of the totalfailure mechanism in the peel of two modified bitumen membranes that areadhesively connected. As defined herein, ‘substrate failure’ is definedas mechanical failure of the substrate while preserving integrity ofboth the adhesive bond and the cohesive bond of the adhesive materialcharacterized by a visual observation noting the presence of substratematerial still adhered to the adhesive material after the test specimenhas been pulled apart. As such, if more than 10% of the surface area ofeach side of the adhesive layer is secured to and covered by a portionof the membrane layer after the adhesively connected membrane layers areseparated from one another, then a substrate failure has occurred.

One non-limiting object of the present invention is the provision of amoisture curable, non-bitumen and non-asphaltic based adhesive that issubstantially free of asphalt, bitumen, coal tar, volatile solvents,and/or isocyanate groups.

Another and/or alternative non-limiting object of the present inventionis the provision of a moisture curable, non-bitumen and non-asphalticbased adhesive that includes extender, compatibilizer and polymer.

Another and/or alternative non-limiting object of the present inventionis the provision of a moisture curable, non-bitumen and non-asphalticbased adhesive that includes extender, compatibilizer and polymer,wherein the polymer includes reactive silyl groups.

Another and/or alternative non-limiting object of the present inventionis the provision of a moisture curable, non-bitumen and non-asphalticbased adhesive that includes extender, compatibilizer and polymer thatis one part adhesive.

Another and/or alternative non-limiting object of the present inventionis the provision of a moisture curable, non-bitumen and non-asphalticbased adhesive that optionally includes one or more of adhesionpromoter, antioxidant, catalyst, dehydration agent, filler and/ortackifier.

Another and/or alternative non-limiting object of the present inventionis the provision of a moisture curable, non-bitumen and non-asphalticbased adhesive that can optionally include one or more other additivessuch as, but not limited to, stabilizer, ultraviolet absorber, metaldeactivator, light stabilizer, thixotropic agent, amine type radicalchain inhibitor, phosphorus-containing peroxide decomposer, lubricant,pigment, foaming agent, anti-foaming agent, flame retardant and/orantistatic agent.

Another and/or alternative non-limiting object of the present inventionis the provision of a moisture curable, non-bitumen and non-asphalticbased adhesive that is formulated to form a peel strength with a roofingmembrane that is greater than 1 pound per linear inch (pli).

Another and/or alternative non-limiting object of the present inventionis the provision of a moisture curable, non-bitumen and non-asphalticbased adhesive that is formulated to form a peel strength with a roofingmembrane of 1-6 pound-force (lbf) after one week of application and1.8-7 lbf after three weeks of application.

Another and/or alternative non-limiting object of the present inventionis the provision of a moisture curable, non-bitumen and non-asphalticbased adhesive that has a tensile strength at point of breakage per ASTMD 413 of at least 70 ksi and up to 250 ksi, and an elongation of atleast 250% and up to 800%.

Another and/or alternative non-limiting object of the present inventionis the provision of a moisture curable, non-bitumen and non-asphalticbased adhesive that has a substrate failure of less than 10% of thetotal failure mechanism in the peel of two modified bitumen membranesthat are adhesively connected.

Another and/or alternative non-limiting object of the present inventionis the provision of a moisture curable, non-bitumen and non-asphalticbased adhesive that comprises at least 4 wt. % extender, at least 2 wt.% compatibilizer, and at least 10 wt. % polymer, and wherein the polymerincludes reactive silyl groups.

Another and/or alternative non-limiting object of the present inventionis the provision of a moisture curable, non-bitumen and non-asphalticbased adhesive that comprises 4-45 wt. % extender, 2-45 wt. %compatibilizer, and 10-31 wt. % polymer, and wherein the polymerincludes reactive silyl groups, and wherein one or more of the reactivesilyl groups in the polymer are selected from the group consisting of apolyether having reactive silyl groups, a polyurethane having reactivesilyl groups, and a polyester having reactive silyl groups.

Another and/or alternative non-limiting object of the present inventionis the provision of a moisture curable, non-bitumen and non-asphalticbased adhesive that further includes one or more of adhesion promoter,antioxidant, catalyst, dehydration agent, filler and/or tackifier.

Another and/or alternative non-limiting object of the present inventionis the provision of a moisture curable, non-bitumen and non-asphalticbased adhesive that includes one or more of at least 0.01 wt. % adhesionpromoter, at least 0.001 wt. % antioxidant, at least 0.1 wt. % catalyst,at least 0.05 wt. % dehydration agent, at least 20 wt. % filler, and/orat least 0.01 wt. % tackifier.

Another and/or alternative non-limiting object of the present inventionis the provision of a moisture curable, non-bitumen and non-asphalticbased adhesive that further includes 0.01-4 wt. % adhesion promoter,0.05-0.5 wt. % antioxidant, 0.05-2 wt. % dehydration agent, 20-70 wt. %filler, and 0.1-1 wt. % catalyst.

Another and/or alternative non-limiting object of the present inventionis the provision of a moisture curable, non-bitumen and non-asphalticbased adhesive that includes 0.01-0.1 wt. % adhesion promoter, 0.05-0.35wt. % antioxidant, 0.05-0.3 wt. % dehydration agent, 20-35 wt. % filler,and 0.1-0.4 wt. % catalyst.

Another and/or alternative non-limiting object of the present inventionis the provision of a moisture curable, non-bitumen and non-asphalticbased adhesive that includes tackifier.

Another and/or alternative non-limiting object of the present inventionis the provision of a moisture curable, non-bitumen and non-asphalticbased adhesive that forms a peel strength of with a roofing membranethat is greater than 1 pli.

Another and/or alternative non-limiting object of the present inventionis the provision of a moisture curable, non-bitumen and non-asphalticbased adhesive that forms a peel strength of with a roofing membranethat is greater than 2 pli.

Another and/or alternative non-limiting object of the present inventionis the provision of a moisture curable, non-bitumen and non-asphalticbased adhesive wherein the weight ratio of said extender to saidcompatibilizer is 1:1 to 5:1.

Another and/or alternative non-limiting object of the present inventionis the provision of a moisture curable, non-bitumen and non-asphalticbased adhesive wherein the compatibilizer includes one or more compoundsselected from the group consisting of adipate glycols, carbonate glycolsparaffinic and olefinic glycols.

Another and/or alternative non-limiting object of the present inventionis the provision of a moisture curable, non-bitumen and non-asphalticbased adhesive wherein the extender includes one or more compoundsselected from the group consisting of polybasic acids and polyhydricalcohols.

Another and/or alternative non-limiting object of the present inventionis the provision of a moisture curable, non-bitumen and non-asphalticbased adhesive wherein the tackifier includes one or more compoundsselected from the group consisting of naphthenic oil and aromaticresins.

Another and/or alternative non-limiting object of the present inventionis the provision of a moisture curable, non-bitumen and non-asphalticbased adhesive wherein the polymer includes an a, 1 telechelicsilyl-terminated polymer.

Another and/or alternative non-limiting object of the present inventionis the provision of an adhered roofing system comprising a) a roofsubstrate; b) a roofing membrane; and c) a cured adhesive, wherein thecured adhesive is a cured product of a moisture curable, non-bitumen andnon-asphaltic based adhesive, and wherein the roof membrane optionallyis a modified bitumen membrane or an EPDM polymer membrane.

These and other objects, features and advantages of the presentinvention will become apparent in light of the following detaileddescription of preferred embodiments thereof, as illustrated in theaccompanying drawing.

BRIEF DESCRIPTION OF THE DRAWING

Reference may now be made to the drawing, which illustrates variousembodiments that the invention may take in physical form and in certainparts and arrangement of parts wherein:

FIG. 1 illustrates examples of different types of failure modes in apeel test, in accordance with at least one possible embodiment.

DETAILED DESCRIPTION OF A NON-LIMITING EMBODIMENT

A more complete understanding of the articles/devices, processes, andcomponents disclosed herein can be obtained by reference to theaccompanying drawings. These FIGURES are merely schematicrepresentations based on convenience and the ease of demonstrating thepresent disclosure, and are, therefore, not intended to indicaterelative size and dimensions of the devices or components thereof and/orto define or limit the scope of the exemplary embodiments.

Although specific terms are used in the following description for thesake of clarity, these terms are intended to refer only to theparticular structure of the embodiments selected for illustration in thedrawings and are not intended to define or limit the scope of thedisclosure. In the drawings and the following description below, it isto be understood that like numeric designations refer to components oflike function.

The singular forms “a,” “an,” and “the” include plural referents unlessthe context clearly dictates otherwise.

As used in the specification and in the claims, the term “comprising”may include the embodiments “consisting of” and “consisting essentiallyof.” The terms “comprise(s),” “include(s),” “having,” “has,” “can,”“contain(s),” and variants thereof, as used herein, are intended to beopen-ended transitional phrases, terms, or words that require thepresence of the named ingredients/steps and permit the presence of otheringredients/steps. However, such description should be construed as alsodescribing compositions or processes as “consisting of” and “consistingessentially of” the enumerated ingredients/steps, which allows thepresence of only the named ingredients/steps, along with any unavoidableimpurities that might result therefrom, and excludes otheringredients/steps.

Numerical values in the specification and claims of this applicationshould be understood to include numerical values which are the same whenreduced to the same number of significant FIGURES and numerical valueswhich differ from the stated value by less than the experimental errorof conventional measurement technique of the type described in thepresent application to determine the value.

All ranges disclosed herein are inclusive of the recited endpoint andindependently combinable (for example, the range of “from 2 grams to 10grams” is inclusive of the endpoints, 2 grams and 10 grams, and all theintermediate values).

The terms “about” and “approximately” can be used to include anynumerical value that can vary without changing the basic function ofthat value. When used with a range, “about” and “approximately” alsodisclose the range defined by the absolute values of the two endpoints,e.g. “about 2 to about 4” also discloses the range “from 2 to 4.”Generally, the terms “about” and “approximately” may refer to plus orminus 10% of the indicated number.

Percentages of elements should be assumed to be percent by weight of thestated element, unless expressly stated otherwise.

While this invention is susceptible of embodiments in many differentforms, there is shown in the drawings and described herein in detailspecific embodiments with the understanding that the present disclosureis to be considered as an exemplification and is not intended to belimited to the embodiments illustrated.

It will be understood that like or analogous elements and/or components,referred to herein, may be identified throughout the drawings by likereference characters. In addition, it will be understood that thedrawings are merely schematic representations of the invention, and someof the components may have been distorted from actual scale for purposesof pictorial clarity.

The proposed embodiments provide an example low cost moisture curable,non-bitumen and non-asphaltic based adhesive. In some non-limitingembodiments, the moisture curable, non-bitumen and non-asphaltic basedadhesive contains a moisture curable polymer having reactive silylgroups or crosslinkable isocyanate endgroups and at least one extenderand compatibilizer that provides a high peel strength useful inasphaltic and rubber-based membranes. The moisture curable, non-bitumenand non-asphaltic based adhesive is also free or substantially free ofcarcinogens such as asphalt, coal tar, and volatile solvents. In onenon-limiting example, the moisture curable, non-bitumen andnon-asphaltic based adhesive is substantially free of volatile organiccompounds. In another non-limiting example, the moisture curable,non-bitumen and non-asphaltic based adhesive is substantially free ofisocyanate groups.

An example one-part, moisture curable, non-bitumen and non-asphalticbased adhesive in accordance with one non-limiting embodiment comprisesa silyl-terminated polymer, an extender, compatibilizer and a catalystfor promoting curing of the silyl-terminated polymer. In someembodiments, other non-limiting ingredients may be included in theone-part, moisture curable, non-bitumen and non-asphaltic basedadhesive, with the other non-limiting ingredients including one or morefillers, tackifiers, antioxidants, ultraviolet absorbers, adhesionpromoters, dehydrating agents, and/or colorants.

In accordance with certain aspects of the embodiments, the moisturecurable, non-bitumen and non-asphaltic based adhesive comprising severalpolymeric and chemical substances undergoes a specific sequence ofchemical reactions and physical changes that result in strong anddurable bonds between certain roof membranes and corresponding rigidconstruction materials. These moisture curable, non-bitumen andnon-asphaltic based adhesives can be roller applied, troweled, orsprayed with airless or conventional spray systems.

In still yet additional and/or alternative non-limiting aspect of theembodiments, the moisture curable, non-bitumen and non-asphaltic basedadhesive can include one or more of a dehydrating agent, compatibilizer,tackifier, stabilizer, filler, antioxidant, adhesion promoter,ultraviolet absorber, metal deactivator, antioxidant, light stabilizer,thixotropic agent, catalyst, amine-type radical chain inhibitor,phosphorus-containing peroxide decomposer, lubricant, pigment, foamingagent, anti-foaming agent, flame retardant and/or antistatic agent. In anon-limiting example, the adhesion promoter is approximately 0.01-1.0wt. % of the moisture curable, non-bitumen and non-asphaltic basedadhesive, the dehydration agent is approximately 0.05-1.5 wt. % of themoisture curable, non-bitumen and non-asphaltic based adhesive, thefiller is approximately 20-35 wt. % of the moisture curable, non-bitumenand non-asphaltic based adhesive, and the catalyst is approximately0.1-1.0 wt. % of the moisture curable, non-bitumen and non-asphalticbased adhesive.

An extender(s) can be utilized that facilitates affinity with both themoisture curable, non-bitumen and non-asphaltic based adhesive and aroofing membrane. The extender is one of the mechanisms used to provideadhesion to the roofing membrane. In a non-limiting form, the extendermay provide viscosity reduction and increased permeability that issuitable for improved workability and adequate cure throughout thematrix of the moisture curable, non-bitumen and non-asphaltic basedadhesive. Extenders suitable for use in the moisture curable,non-bitumen and non-asphaltic based adhesive can include esters ofpolybasic acids and polyhydric alcohol, or fatty acid oils/esters,and/or aromatic/aliphatic carboxylic acid esters, among others. Suitableextenders include, but are not limited to, triethylene glycoldi-(2-ethylbutyrate), triethylene glycol di-(2-ethylhexanoate),triethylene glycol diheptanoate, tetraethylene glycol diheptanoate,dihexyl adipate, dioctyl adipate, hexyl cyclohexyladipate, mixtures ofheptyl and nonyl adipates, diisononyl adipate, heptyl nonyl adipate,dibutyl sebacate, isononyl benzoate, nonyl benzoate, isodecyl benzoate,decyl benzoate, 2-propylheptyl benzoate, isoundecylbenzoate, isotridecylbenzoate, di-heptyl cyclohexanoate, di-2-ethylhexyl cyclohexanoate,di-n-nonyl cyclohexanoate, diisononyl cyclohexanoate, di-n-decylcyclohexanoate, diisodecyl cyclohexanoate, di-2-propyl heptylcyclohexanoate, diheptyl adipate, dioctyl adipate, diisononyl adipate,diisodecyl adipate, di 2-propylheptyl adipate, dipropylene glycoldibenzoate, diethylene glycol dibenzoate, triethylene glycol dibenzoate,or mixtures thereof. Generally, the extender is used in the range of5-40 wt. % of the moisture curable, non-bitumen and non-asphaltic basedadhesive. In a non-limiting embodiment, the extender is at least 4 wt. %of the moisture curable, non-bitumen and non-asphaltic based adhesive.

A non-limiting component of the moisture curable, non-bitumen andnon-asphaltic based adhesive uses processing oil(s) as a tackifier thatincludes virtually any hydrocarbon oil or mixture thereof that iscommonly used in bitumen and/or coal tar compounding or as a plasticizerand processing aid, such as a naphthenic oil or aromatic resinscontaining varying aromatic contents, such as aromatic resins, can beused but is not necessary. The tackifier should be compatible with othercomponents of the moisture curable, non-bitumen and non-asphaltic basedadhesive. Specific, non-limiting examples of such aromatic resinsinclude C9, C5, and coumarone indene resins. Specific, non-limitingexamples of suitable naphthenic oils include Sundex 790T from Sunoco,ProGuard Altranap 1000 from Lynden Oil Co., and Amplex® 100 from Citgo.The tackifier (when used) can be about 0.1-30 wt. % (and all values andranges therebetween) of the moisture curable, non-bitumen andnon-asphaltic based adhesive, typically about 0.5-5 wt. %, and moretypically about 1-3 wt. %.

An antioxidant(s) can optionally be used in the moisture curable,non-bitumen and non-asphaltic based adhesive. The antioxidant can beused to further improve the stability of the moisture curable,non-bitumen and non-asphaltic based adhesive. The antioxidants (whenused) can be about 0.01-5 wt. % moisture curable, non-bitumen andnon-asphaltic based adhesive (and all values and ranges therebetween) ofthe moisture curable, non-bitumen and non-asphaltic based adhesive, andtypically about 0.1-1 wt. %. Non-limiting antioxidants include Irgonox®1010 (BASF), CYASORB® (Cytec) Ultraviolet (UV) stabilizers.

A catalyst(s) can optionally be used in the moisture curable,non-bitumen and non-asphaltic based adhesive. One non-limiting catalystis dibutyltin dilaurate. The addition of a catalyst can be used tocontrol reaction speed during the curing of the moisture curable,non-bitumen and non-asphaltic based adhesive. Care needs to be takenwhen using catalysts because of gelation risks. Generally, no more than1 wt. % of catalyst is recommended, e.g., 0.01-1 wt. % and all valuesand ranges therebetween. Non-limiting catalysts that can be used innon-bitumen based adhesive include dibutyltin dilaurate, dibutyltinoxide, dimethylcyclohexylamine (DMCHA), dimethylethanolamine (DMEA),dioctyltin mercaptide, and N-tin mercaptides.

Examples of moisture cure silyl-terminated polymers that may be used inthe moisture curable, non-bitumen and non-asphaltic based adhesiveinclude silylated polyurethane, silylated polyethers, silylatedacrylics, and silylated polyesters. The silylated polymers orsilyl-terminated polymers of the embodiments include two or morereactive silyl groups, with alpha, omega-telechelic silane-terminatedpolymers being preferred. In a non-limiting example, the polymer isapproximately 10-31 wt. % of the moisture curable, non-bitumen andnon-asphaltic based adhesive, and the polymer includes reactive silylgroups.

Examples of moisture cure isocyanate terminated polymers that may beused in the moisture curable, non-bitumen and non-asphaltic basedadhesive include any moisture curable polyurethane or polyureaprepolymer comprised of excess isocyanate reacted with one or moreactive hydrogen-containing molecules.

Examples of active hydrogen-containing molecules useful in thepreparation of polyurethane prepolymers include, but are not limited to,either one or a combination of polyether, polyester, or polyalkyldienepolyols, or derived from reaction of excess of such polyols, alone or incombination with isocyanate functional compounds. The polyols can bediols or triols, preferably, polyether diols are used. Representativeexamples of useful polyols include polyoxypropylene polyol, polyalkylenepolyol, and polypropylene glycols. In one non-limiting example,polyether diols having high equivalent weights are used. For example,polyether diols with equivalent weights ranging from greater than about200 to about 20000, and typically about 500 to about 5000 can be used.

Examples of active hydrogen-containing molecules useful in thepreparation of polyurea prepolymers include, but are not limited to,either one or a combination of primary or secondary amine functionalpolyether, polyester, or polyalkyldiene polymers, or derived fromreaction of excess of such primary amine functional polymers, alone orin combination withisocyanate functional compounds. The amine functionalpolymers can be either difunctional or trifunctional. In onenon-limiting embodiment, polyether diamines are used. Representativeexamples of useful amine functional polymers are polyoxypropyleneamine,polyalkyleneamine, and amine terminated polypropylene glycols. Polyetherdiamines having high equivalent weights can be used. For example,polyether diamines with equivalent weights ranging from greater thanabout 200 to about 20000, and typically 500-5000 can be used.

The fillers optionally used in the moisture curable, non-bitumen andnon-asphaltic based adhesive can include, but are not limited to, woodmeal, walnut shell flour, rice hull flour, pulp, cotton chips, mica,graphite, diatomaceous earth, china clay, kaolin, clay, talc, fumedsilica, precipitated silica, silicic anhydride, quartz powder, glassbeads, calcium carbonate, magnesium carbonate, titanium oxide, carbonblack, glass balloons, aluminum powder, zinc powder, asbestos, glassfiber and carbon fiber. The above fillers can be used individually or incombination.

The limited compatibility of adhesive polymers and extenders withbitumen/asphaltic roofing products often leads to unstable and/or tooaggressive membrane penetration and thereby results in variable and/orinferior long term adhesion properties. Compatibilizers of moderatelypolar component can be used to compatibilize dissimilar materials andhave been found, when used in the moisture curable, non-bitumen andnon-asphaltic based adhesive, to result in stable mixtures and goodadhesion and stability properties of the membrane. Examples ofcompatibilizers include, but are not limited to, adipate and carbonateglycols and olefinic glycols. Generally, the compatibilizer is at least2 wt. % of the moisture curable, non-bitumen and non-asphaltic basedadhesive. In one non-limiting embodiment, a weight ratio between theextender and the compatibilizer in the moisture curable, non-bitumen andnon-asphaltic based adhesive is about 1:1 to 5:1.

Suitable polyols that can be used as the compatibilizer include one ormore of polyoxyalkylene polyols, also called polyether polyols oroligoetherols, which are polymerization products of ethylene oxide,1,2-propylene oxide, 1,2- or 2,3-butylene oxide, oxetane,tetrahydrofuran or mixtures thereof, possibly polymerized with the aidof a starter molecule having two or more active hydrogen atoms, forexample water, ammonia or compounds having a plurality ofoxygen-hydrogen (OH) or nitrogen-hydrogen (NH) groups.

Referring now to FIG. 1, there are three examples of failure mode of anadhesive. Failure mode is defined as the mechanism of mechanical and/oradhesive bond failure within a test specimen. As an example, all testspecimens represented in the Tables 1-4 were constructed from two 1″×6″sections of GAF Tri Ply SBS Granule modified bitumen membrane, and thetwo 1″×6″ sections of modified bitumen membrane were adhered togetherusing the moisture curable, non-bitumen and non-asphaltic based adhesiveidentified in the eighteen (18) set forth below. One-inch wide specimenswere tested at a rate, both crosshead and chart speed, of two inches perminute using the adhesion test method set forth in American Section ofthe International Association for Testing Materials (ASTM) D-413 machinemethod. Failure mode of the test specimens was determined at a roomtemperature of approximately 23° C. In this context, the failure mode issummed into four categories.

First, adhesive failure 100 is defined as a failure of the adhesive bondat an interface between the adhesive material and a substratecharacterized by a visual observation noting absence of adhesivematerial on at least one of the bonded surfaces of the test specimen.Second, cohesive failure 200 is defined as mechanical failure of theadhesive material while preserving the adhesive bond to the substratecharacterized by a visual observation noting presence of the adhesivematerial on both bonded surfaces of the test specimen. Third,cohesive/adhesive failure is defined as a combination of mechanicalfailure in the adhesive material and adhesive bond failure at theinterface of the adhesive material and the substrate characterized by avisual observation noting a mixture of both adhesive failure 100 andcohesive failure 200 on the bonded surfaces of the test specimen.Fourth, substrate failure 300 is defined as mechanical failure of thesubstrate while preserving integrity of both the adhesive bond and thecohesive bond of the adhesive material characterized by a visualobservation noting the presence of substrate material still adhered tothe adhesive material after the test specimen has been pulled apart.Adhesive failure 100 and cohesive failure 200 are primarily desired dueto the fact that an adhesive composition which solubilizes the modifiedbitumen membrane too aggressively will compromise the integrity of thesubstrate, which is signified by the substrate failure 300 mode. Amoisture curable, non-bitumen and non-asphaltic based adhesive isconsidered passing if the substrate failure 300 is less than 10% of thetotal failure mechanism in the peel.

Viscosity data was gathered for the moisture curable, non-bitumen andnon-asphaltic based adhesive listed in examples 1-18 on an RVTBrookfield Viscometer using a C spindle at 1, 2 and 10 rotations perminute. Tensile strength and elongation were measured for the moisturecurable, non-bitumen and non-asphaltic based adhesive listed in examples1-18 in accordance with ASTM D 412 Method A using an Instron TensileTester. Sample securement was achieved through the use of pneumaticclamps which provide 200 psi force to minimize slippage of the testspecimen during actual testing.

The following examples of moisture curable, non-bitumen andnon-asphaltic based adhesive illustrate the embodiments in furtherdetail, but do not limit the scope of the embodiments.

Example 1 is a single component, moisture curable, non-bitumen andnon-asphaltic based adhesive for asphaltic membrane bonding from Tables1-4, in accordance with the embodiments, was prepared in a formulautilizing the following ingredients and parts:

Polymer Momentive Y-15990 (SPUR) 15.00 Compatibilizer PPG 725(Polypropylene glycol) 10.00 Extender Diisononyl Phthalate 15.00 FillerG3T (CaCO3) 57.00 Antioxidant Irganox 245 0.25 Dehydration Agent VTMO1.25 Adhesion Promoter DAMO-T 1.00 Catalyst DBTDL 0.50

Example 2 is a single component, moisture curable, non-bitumen andnon-asphaltic based adhesive for asphaltic membrane bonding from Tables1-4, in accordance with the embodiments, was prepared in a formulautilizing the following ingredients and parts:

Polymer Momentive Y-15990 (SPUR) 15.00 Compatibilizer PPG 725(Polypropylene glycol) 10.00 Extender Eastman 168 (Dioctylterephthalate) 15.00 Filler G3T (CaCO3) 57.00 Antioxidant Irganox 2450.25 Dehydration Agent VTMO 1.25 Adhesion Promoter DAMO-T 1.00 CatalystDBTDL 0.50

Example 3 is a single component, moisture curable, non-bitumen andnon-asphaltic based adhesive for asphaltic membrane bonding from Tables1-4, in accordance with the embodiments, was prepared in a formulautilizing the following ingredients and parts:

Polymer Kaneka SAX 350 (STPE) 15.00 Compatibilizer PPG 725(Polypropylene glycol) 10.00 Extender Eastman 168 (Dioctylterephthalate) 15.00 Filler G3T (CaCO3) 57.00 Antioxidant Irganox 2450.25 Dehydration Agent VTMO 1.25 Adhesion Promoter DAMO-T 1.00 CatalystDBTDL 0.50

Example 4 is single component, moisture curable, non-bitumen andnon-asphaltic based adhesive for asphaltic membrane bonding from Tables1-4, in accordance with the embodiments, was prepared in a formulautilizing the following ingredients and parts:

Polymer Momentive Y-15990 (SPUR) 15.00 Compatibilizer PPG 725(Polypropylene glycol) 10.00 Extender tri(ethylene glycol)bis(2-ethylhexanoate) 15.00 Filler G3T (CaCO3) 57.00 Antioxidant Irganox245 0.25 Dehydration Agent VTMO 1.25 Adhesion Promoter DAMO-T 1.00Catalyst DBTDL 0.50

Example 5 is a single component, moisture curable, non-bitumen andnon-asphaltic based adhesive for asphaltic membrane bonding from Tables1-4, in accordance with the embodiments, was prepared in a formulautilizing the following ingredients and parts:

Polymer Momentive Y-15990 (SPUR) 15.00 Compatibilizer PPG 725(Polypropylene glycol) 10.00 Extender Bis(2-ethylhexyl) sebacate 15.00Filler G3T (CaCO3) 57.00 Antioxidant Irganox 245 0.25 Dehydration AgentVTMO 1.25 Adhesion Promoter DAMO-T 1.00 Catalyst DBTDL 0.50

Example 6 is a single component, moisture curable, non-bitumen andnon-asphaltic based adhesive for asphaltic membrane bonding from Tables1-4, in accordance with the embodiments, was prepared in a formulautilizing the following ingredients and parts:

Polymer Kaneka SAX 350 (STPE) 15.00 Compatibilizer PPG 725(Polypropylene glycol) 10.00 Extender Bis(2-ethylhexyl) sebacate 15.00Filler G3T (CaCO3) 57.00 Antioxidant Irganox 245 0.25 Dehydration AgentVTMO 1.25 Adhesion Promoter DAMO-T 1.00 Catalyst DBTDL 0.50

Example 7 is a single component, moisture curable, non-bitumen andnon-asphaltic based adhesive for asphaltic membrane bonding from Tables1-4, in accordance with the embodiments, was prepared in a formulautilizing the following ingredients and parts:

Polymer Momentive Y-15990 (SPUR) 15.00 Compatibilizer C-1090(Polycarbonate polyol) 10.00 Extender Diisononyl Phthalate 15.00 FillerG3T (CaCO3) 57.00 Antioxidant Irganox 245 0.25 Dehydration Agent VTMO1.25 Adhesion Promoter DAMO-T 1.00 Catalyst DBTDL 0.50

Example 8 is a single component, moisture curable, non-bitumen andnon-asphaltic based adhesive for asphaltic membrane bonding from Tables1-4, in accordance with the embodiments, was prepared in a formulautilizing the following ingredients and parts:

Polymer Momentive Y-15990 (SPUR) 15.00 Compatibilizer C-1090(Polycarbonate polyol) 10.00 Extender Eastman 168 (Dioctylterephthalate) 15.00 Filler G3T (CaCO3) 57.00 Antioxidant Irganox 2450.25 Dehydration Agent VTMO 1.25 Adhesion Promoter DAMO-T 1.00 CatalystDBTDL 0.50

Example 9 is a single component, moisture curable, non-bitumen andnon-asphaltic based adhesive for asphaltic membrane bonding from Tables1-4, in accordance with the embodiments, was prepared in a formulautilizing the following ingredients and parts:

Polymer Kaneka SAX 350 (STPE) 15.00 Compatibilizer C-1090 (Polycarbonatepolyol) 10.00 Extender Eastman 168 (Dioctyl terephthalate) 15.00 FillerG3T (CaCO3) 57.00 Antioxidant Irganox 245 0.25 Dehydration Agent VTMO1.25 Adhesion Promoter DAMO-T 1.00 Catalyst DBTDL 0.50

Example 10 is a single component, moisture curable, non-bitumen andnon-asphaltic based adhesive for asphaltic membrane bonding from Tables1-4, in accordance with the embodiments, was prepared in a formulautilizing the following ingredients and parts:

Polymer Momentive Y-15990 (SPUR) 15.00 Compatibilizer C-1090(Polycarbonate polyol) 10.00 Extender tri(ethylene glycol)bis(2-ethylhexanoate) 15.00 Filler G3T (CaCO3) 57.00 Antioxidant Irganox245 0.25 Dehydration Agent VTMO 1.25 Adhesion Promoter DAMO-T 1.00Catalyst DBTDL 0.50

Example 11 is a single component, moisture curable, non-bitumen andnon-asphaltic based adhesive for asphaltic membrane bonding from Tables1-4, in accordance with the embodiments, was prepared in a formulautilizing the following ingredients and parts:

Polymer Momentive Y-15990 (SPUR) 15.00 Compatibilizer C-1090(Polycarbonate polyol) 10.00 Extender Bis(2-ethylhexyl) sebacate 15.00Filler G3T (CaCO3) 57.00 Antioxidant Irganox 245 0.25 Dehydration AgentVTMO 1.25 Adhesion Promoter DAMO-T 1.00 Catalyst DBTDL 0.50

Example 12 is a single component, moisture curable, non-bitumen andnon-asphaltic based adhesive for asphaltic membrane bonding from Tables1-4, in accordance with the embodiments, was prepared in a formulautilizing the following ingredients and parts:

Polymer Kaneka SAX 350 (STPE) 15.00 Compatibilizer C-1090 (Polycarbonatepolyol) 10.00 Extender Bis(2-ethylhexyl) sebacate 15.00 Filler G3T(CaCO3) 57.00 Antioxidant Irganox 245 0.25 Dehydration Agent VTMO 1.25Adhesion Promoter DAMO-T 1.00 Catalyst DBTDL 0.50

Example 13 is a single component, moisture curable, non-bitumen andnon-asphaltic based adhesive for asphaltic membrane bonding from Tables1-4, in accordance with the embodiments, was prepared in a formulautilizing the following ingredients and parts:

Polymer Momentive Y-15990 (SPUR) 15.00 Compatibilizer P-1010 (Adipateglycol) 10.00 Extender Diisononyl Phthalate 15.00 Filler G3T (CaCO3)57.00 Antioxidant Irganox 245 0.25 Dehydration Agent VTMO 1.25 AdhesionPromoter DAMO-T 1.00 Catalyst DBTDL 0.50

Example 14 is a single component, moisture curable, non-bitumen andnon-asphaltic based adhesive for asphaltic membrane bonding from Tables1-4, in accordance with the embodiments, was prepared in a formulautilizing the following ingredients and parts:

Polymer Momentive Y-15990 (SPUR) 15.00 Compatibilizer P-1010 (Adipateglycol) 10.00 Extender Eastman 168 (Dioctyl terephthalate) 15.00 FillerG3T (CaCO3) 57.00 Antioxidant Irganox 245 0.25 Dehydration Agent VTMO1.25 Adhesion Promoter DAMO-T 1.00 Catalyst DBTDL 0.50

Example 15 is a single component, moisture curable, non-bitumen andnon-asphaltic based adhesive for asphaltic membrane bonding from Tables1-4, in accordance with the embodiments, was prepared in a formulautilizing the following ingredients and parts:

Polymer Kaneka SAX 350 (STPE) 15.00 Compatibilizer P-1010 (Adipateglycol) 10.00 Extender Eastman 168 (Dioctyl terephthalate) 15.00 FillerG3T (CaCO3) 57.00 Antioxidant Irganox 245 0.25 Dehydration Agent VTMO1.25 Adhesion Promoter DAMO-T 1.00 Catalyst DBTDL 0.50

Example 16 is a single component, moisture curable, non-bitumen andnon-asphaltic based adhesive for asphaltic membrane bonding from Tables1-4, in accordance with the embodiments, was prepared in a formulautilizing the following ingredients and parts:

Polymer Momentive Y-15990 (SPUR) 15.00 Compatibilizer P-1010 (Adipateglycol) 10.00 Extender tri(ethylene glycol) bis(2-ethylhexanoate) 15.00Filler G3T (CaCO3) 57.00 Antioxidant Irganox 245 0.25 Dehydration AgentVTMO 1.25 Adhesion Promoter DAMO-T 1.00 Catalyst DBTDL 0.50

Example 17 is a single component, moisture curable, non-bitumen andnon-asphaltic based adhesive for asphaltic membrane bonding from Tables1-4, in accordance with the embodiments, was prepared in a formulautilizing the following ingredients and parts:

Polymer Momentive Y-15990 (SPUR) 15.00 Compatibilizer P-1010 (Adipateglycol) 10.00 Extender Bis(2-ethylhexyl) sebacate 15.00 Filler G3T(CaCO3) 57.00 Antioxidant Irganox 245 0.25 Dehydration Agent VTMO 1.25Adhesion Promoter DAMO-T 1.00 Catalyst DBTDL 0.50

Example 18 is a single component, moisture curable, non-bitumen andnon-asphaltic based adhesive for asphaltic membrane bonding from Tables1-4, in accordance with the embodiments, was prepared in a formulautilizing the following ingredients and parts:

Polymer Kaneka SAX 350 (STPE) 15.00 Compatibilizer P-1010 (Adipateglycol) 10.00 Extender Bis(2-ethylhexyl) sebacate 15.00 Filler G3T(CaCO3) 57.00 Antioxidant Irganox 245 0.25 Dehydration Agent VTMO 1.25Adhesion Promoter DAMO-T 1.00 Catalyst DBTDL 0.50

Examples 1-18 prepared from the moisture curable, non-bitumen andnon-asphaltic based adhesive listed above are identified as Examples1-18 in Table 1 below. Table 1 shows a comparison of peel adhesionproperties obtained on GAF Tri Ply SBS Granule modified bitumen membraneusing the moisture curable, non-bitumen and non-asphaltic based adhesiveidentified in Examples 1-18.

TABLE 1 Adhesion Peel Data ASTM D 413 1 week 3 week Example 1 3.84 lbf4.74 lbf Example 2 3.62 lbf 4.92 lbf Example 3 4.56 lbf 4.75 lbf Example4 3.95 lbf 4.01 lbf Example 5 3.83 lbf 3.84 lbf Example 6 4.71 lbf 4.78lbf Example 7 1.75 lbf 2.93 lbf Example 8 2.24 lbf 2.33 lbf Example 93.67 lbf 3.83 lbf Example 10 4.01 lbf 3.26 lbf Example 11 2.08 lbf 2.67lbf Example 12 4.66 lbf 3.95 lbf Example 13 1.85 lbf 2.55 lbf Example 141.91 lbf 2.19 lbf Example 15 2.19 lbf 2.73 lbf Example 16 2.66 lbf 2.12lbf Example 17 1.90 lbf 3.20 lbf Example 18 2.94 lbf 3.81 lbf

Examples 1-18 prepared from the moisture curable, non-bitumen andnon-asphaltic based adhesive listed in the Examples are identified asExamples 1-18 in Table 2 below. Table 2 shows a comparison of failuremodes for each test specimen obtained on GAF Tri Ply SBS Granulemodified bitumen membrane using the moisture curable, non-bitumen andnon-asphaltic based adhesive identified in Examples 1-18.

TABLE 2 Failure Mode ASTM D 413 1 week 3 week Example 1 Adhesive FailureAdhesive Failure Example 2 Adhesive Failure Adhesive Failure Example 3Cohesive Failure Cohesive Failure Example 4 Adhesive Failure AdhesiveFailure Example 5 Adhesive Failure Adhesive Failure Example 6 AdhesiveFailure Adhesive Failure Example 7 Adhesive Failure Adhesive FailureExample 8 Adhesive Failure Adhesive Failure Example 9 Adhesive FailureAdhesive Failure Example 10 Adhesive Failure Adhesive Failure Example 11Adhesive Failure Adhesive Failure Example 12 Adhesive Failure AdhesiveFailure Example 13 Adhesive Failure Adhesive Failure Example 14 AdhesiveFailure Adhesive Failure Example 15 Adhesive Failure Adhesive FailureExample 16 Adhesive Failure Adhesive Failure Example 17 Adhesive FailureAdhesive Failure Example 18 Cohesive Failure Cohesive/Adhesive Failure

Examples 1-18 prepared from the moisture curable, non-bitumen andnon-asphaltic based adhesive listed in the Examples are identified asExamples 1-18 in Table 3 below. Table 3 shows a comparison ofviscosities for each moisture curable, non-bitumen and non-asphalticbased adhesive identified in Examples 1-18 on an RVT BrookfieldViscometer using a C spindle at 1,2 and 10 rpms.

TABLE 3 Viscosity Data Brookfield 1 rpm (cP) 2 rpm (cP) 10 rpm (cP)Example 1 71,000 51,500 28,100 Example 2 87,000 62,000 29,500 Example 360,000 38,000 14,500 Example 4 77,000 50,000 20,000 Example 5 73,00048,500 21,300 Example 6 47,000 30,000 11,500 Example 7 261,000 184,000NA Example 8 291,000 209,500 NA Example 9 210,000 129,000 48,200 Example10 200,000 135,000 60,700 Example 11 193,000 129,500 57,700 Example 12170,000 99,000 37,200 Example 13 103,000 74,000 31,700 Example 14119,000 83,000 37,600 Example 15 114,000 71,000 27,700 Example 16 86,00054,000 24,000 Example 17 85,000 60,000 27,100 Example 18 90,000 50,50019,100

Examples 1-18 prepared from the moisture curable, non-bitumen andnon-asphaltic based adhesive are identified as Examples 1-18 in Table 4below. Table 4 shows a comparison of modulus at 100% elongation, tensileat break and ultimate elongation using the moisture curable, non-bitumenand non-asphaltic based adhesive identified in Examples 1-18 inaccordance with ASTM D 412 Method A using Table Model 3345 InstronUniversal Tester.

TABLE 4 Tensile/Elongation ASTM D 413 M100 (psi) Tensile at break (psi)Elongation (%) Example 1 52 138 555 Example 2 56 146 616 Example 3 56 89377 Example 4 55 128 613 Example 5 60 143 611 Example 6 50 85 420Example 7 45 110 588 Example 8 61 125 602 Example 9 69 80 407 Example 1056 115 639 Example 11 66 127 626 Example 12 70 80 424 Example 13 54 135715 Example 14 59 132 689 Example 15 53 56 199 Example 16 50 114 621Example 17 58 116 632 Example 18 58 72 383

The following comparative examples illustrate the invention in furtherdetail, but do not limit the scope of the embodiments. A comparativeexample of a single component, moisture curable, non-bitumen andnon-asphaltic based adhesive for asphaltic membrane bonding inaccordance with the embodiments was prepared in a formula utilizing thefollowing ingredients:

Comparative Example 1 Parts Polymer Momentive Y-15990 (SPUR) 15.00Compatibilizer PPG 725 (Polypropylene glycol) 2.5 Extender DiisononylPhthalate 15.00 Filler G3T (CaCO3) 57.00 Antioxidant Irganox 245 0.25Dehydration Agent VTMO 1.25 Adhesion Promoter DAMO-T 1.00 Catalyst DBTDL0.50

A comparative example of a single component, moisture curable,non-bitumen and non-asphaltic based adhesive for asphaltic membranebonding in accordance with the invention was prepared in a formulautilizing the following ingredients:

Comparative Example 2 Parts Polymer Momentive Y-15990 (SPUR) 15.00Compatibilizer PPG 725 (Polypropylene glycol) 0.0 Extender DiisononylPhthalate 15.00 Filler G3T (CaCO3) 57.00 Antioxidant Irganox 245 0.25Dehydration Agent VTMO 1.25 Adhesion Promoter DAMO-T 1.00 Catalyst DBTDL0.50

Adhesion peel data for Comparative Examples 1 and 2 is listed in Table 5below. All adhesion peel specimens were constructed and tested inaccordance with the adhesion peel test procedure defined above usingASTM D 413.

TABLE 5 Adhesion Peel Data ASTM D 413 1 week 3 week Comparative Example1 4.78 lbf 4.89 lbf Comparative Example 2 3.32 lbf 5.54 lbf

Table 6 shows a comparison of failure modes for each test specimenobtained on GAF Tri Ply SBS Granule modified bitumen membrane using themoisture curable, non-bitumen and non-asphaltic based adhesiveidentified in Comparative Examples 1 and 2. Failure mode was tested andevaluated in accordance with the definition outlined above using ASTM D413.

TABLE 6 Failure Mode ASTM D 413 1 week 3 week Comparative Example 1Adhesive Failure 90% Adhesive Failure/ 10% Substrate Failure ComparativeExample 2 80% Adhesive Failure/ 40% Adhesive Failure/ 20% SubstrateFailure 60% Substrate Failure

As can be seen in Table 6 above Comparative Examples 1 and 2 bothdemonstrated substrate failure after three weeks of conditioning underambient temperature (i.e. approximately 23 degrees Celsius). After oneweek of conditioning, only Comparative Example 2 showed signs ofsubstrate failure demonstrating an inverse correlation between migrationof the extender and the loading level of compatibilizer in the moisturecurable, non-bitumen and non-asphaltic based adhesive.

The identity, manufacturer and location of all ingredients used inExamples 1-18 and Comparative Examples 1 and 2 are identified below inTable 7.

TABLE 7 Ingredient Manufacturer Location STPE (SAX 350) Kaneka JapanSPUR (Y-15990) Momentive United States Polypropylene glycol (PPG 725)Covestro United States Adipate glycol (P-1010) Kuraray JapanPolycarbonate polyol (C-1090) Kuraray Japan Diisononyl Phthalate(Plasthall DINP) Hallstar United States Dioctyl terephthalate (Eastman168) Eastman United States Triethylene glycol bis Sigma Aldrich UnitedStates (2-ethylhexanoate) Bis(2-ethylhexyl)sebacate Sigma Aldrich UnitedStates Calcium Carbonate (G3T) Huber United States Antioxidant (Irganox245) BASF United States 10 Vinyltrimethoxysilane (VTMO) Momentive UnitedStates Aminosilane (DAMO-T) Momentive United States Dibutyltin dilaurate(Dabco T-12) Galata Chem. United States

The foregoing description merely explains and illustrates the inventionand the invention is not limited thereto except insofar as the appendedclaims are so limited, as those skilled in the art who have thedisclosure before them will be able to make modifications withoutdeparting from the scope of the invention.

While considerable emphasis has been placed herein on the structures andconfigurations of the preferred embodiments of the invention, it will beappreciated that other embodiments, as well as modifications of theembodiments disclosed herein, can be made without departing from theprinciples of the invention. These and other modifications of thepreferred embodiments, as well as other embodiments of the invention,will be obvious and suggested to those skilled in the art from thedisclosure herein, whereby it is to be distinctly understood that theforegoing descriptive matter is to be interpreted merely as illustrativeof the present invention and not as a limitation thereof.

1-24. (canceled)
 25. A moisture curable adhesive comprising extender,compatibilizer, polymer, and less than 0.5 wt. % of a compound selectedfrom the group consisting of asphalt, bitumen, and coal tar; saidpolymer including reactive silyl groups; said moisture curable adhesiveincluding less than 0.5 wt. % volatile organic compounds; said moisturecurable adhesive including less than 0.5 wt. % isocyanate groups. 26.The moisture curable adhesive as defined in claim 25, wherein saidmoisture curable adhesive comprises at least 4 wt. % extender, at least2 wt. % compatibilizer, at least 10 wt. % polymer.
 27. The moisturecurable adhesive as defined in claim 25, wherein said moisture curableadhesive comprises 4-45 wt. % extender, 2-45 wt. % compatibilizer, and10-31 wt. % polymer, one or more of said reactive silyl groups in saidpolymer are selected from the group consisting of a polyether havingreactive silyl groups, a polyurethane having reactive silyl groups, anda polyester having reactive silyl groups.
 28. The moisture curableadhesive as defined in claim 25, wherein a weight ratio of said extenderto said compatibilizer is 1:1 to 5:1.
 29. The moisture curable adhesiveas defined in claim 25, wherein said compatibilizer includes one or morecompounds selected from the group consisting of adipate glycols,carbonate glycols paraffinic and olefinic glycols; said extenderincludes one or more compounds selected from the group consisting ofpolybasic acids and polyhydric alcohols.
 30. The moisture curableadhesive as defined in claim 25, wherein said moisture curable adhesiveincludes one or more of at least 0.01 wt. % adhesion promoter, at least0.001 wt. % antioxidant, at least 0.1 wt. % catalyst, at least 0.05 wt.% dehydration agent, at least 20 wt. % filler, and/or at least 0.01 wt.% tackifier.
 31. The moisture curable adhesive as defined in claim 25,wherein said moisture curable adhesive comprises 10-31 wt. % polymer,4-45 wt. % extender, 2-45 wt. % compatibilizer, 0.01-4 wt. % adhesionpromoter, 0.001-5 wt. % antioxidant, 0.01-1 wt. % catalyst, 0.05-2 wt. %dehydration agent, 20-70 wt. % filler.
 32. The moisture curable adhesiveas defined in claim 25, wherein said polymer includes an α, Ω telechelicsilyl-terminated polymer
 33. The moisture curable adhesive as defined inclaim 25, wherein said moisture curable adhesive forms a peel strengthwith a roofing membrane that is greater than 1 pli.
 34. The moisturecurable adhesive as defined in claim 25, wherein said moisture curableadhesive is a single composite adhesive.
 35. An adhered roofing systemcomprising: i. a roof substrate; ii. a roofing membrane; and iii. acured adhesive, said cured adhesive is a cured product of a moisturecurable adhesive comprising extender, compatibilizer, polymer, and lessthan 0.5 wt. % of a compound selected from the group consisting ofasphalt, bitumen, and coal tar; said polymer including reactive silylgroups; said moisture curable adhesive including less than 0.5 wt. %volatile organic compounds; said moisture curable adhesive includingless than 0.5 wt. % isocyanate groups.
 36. The adhered roofing system asdefined in claim 35, wherein said moisture curable adhesive comprises atleast 4 wt. % extender, at least 2 wt. % compatibilizer, at least 10 wt.% polymer.
 37. The adhered roofing system as defined in claim 35,wherein said moisture curable adhesive comprises 4-45 wt. % extender,2-45 wt. % compatibilizer, and 10-31 wt. % polymer, one or more of saidreactive silyl groups in said polymer are selected from the groupconsisting of a polyether having reactive silyl groups, a polyurethanehaving reactive silyl groups, and a polyester having reactive silylgroups.
 38. The adhered roofing system as defined in claim 35, wherein aweight ratio of said extender to said compatibilizer is 1:1 to 5:1. 39.The adhered roofing system as defined in claim 35, wherein saidcompatibilizer includes one or more compounds selected from the groupconsisting of adipate glycols, carbonate glycols paraffinic and olefinicglycols; said extender includes one or more compounds selected from thegroup consisting of polybasic acids and polyhydric alcohols.
 40. Theadhered roofing system as defined in claim 35, wherein said moisturecurable adhesive includes one or more of at least 0.01 wt. % adhesionpromoter, at least 0.001 wt. % antioxidant, at least 0.1 wt. % catalyst,at least 0.05 wt. % dehydration agent, at least 20 wt. % filler, and/orat least 0.01 wt. % tackifier.
 41. The adhered roofing system as definedin claim 35, wherein said moisture curable adhesive comprises 10-31 wt.% polymer, 4-45 wt. % extender, 2-45 wt. % compatibilizer, 0.01-4 wt. %adhesion promoter, 0.001-5 wt. % antioxidant, 0.01-1 wt. % catalyst,0.05-2 wt. % dehydration agent, 20-70 wt. % filler.
 42. The adheredroofing system as defined in claim 35, wherein said polymer includes anα, Ω telechelic silyl-terminated polymer
 43. The adhered roofing systemas defined in claim 35, wherein said moisture curable adhesive forms apeel strength with a roofing membrane that is greater than 1 pli. 44.The adhered roofing system as defined in claim 35, wherein said roofmembrane is a modified bitumen membrane or an EPDM polymer membrane. 45.The adhered roofing system as defined in claim 35, wherein said moisturecurable adhesive is a single composite adhesive.